Emollient compositions



was A r-.8, i946 7 2,398,296,

umrspf s'mrss PATENT oFr c-E 2,398,296

EMOIJJENT COMPOSITIONS Albert K. Epstein and Morris Katzman, Chicago,

11]., assignors to The Emnlsol Corporation; Ohicago, lll., a corporation of Illinois I No Drawing. Application April 1, 1943. v

' I Serial No. 481,466.

is Claims. (01. 167-96) This invention relates to novel and useful co'mbon atoms, A is an anion, preferably of a solubilpositions for the preparation of emollients such izing character and preferably halogen, '1 is (l) as hand lotions, shavingdotions and the like and a member of the group NHR' where R is hydroto the latter compositions. gen, lower alkyl, hydroxyaikyl, and 'cycloalkyl, or It has heretofore been suggested to prepare 5 (2) OY'Where Y'is a cation,-lower alkyl, cycloemoliient compositions, in the form of aqueous alkyl or an aliphatic polyhydric alcohol radical.- dispersions or ol'eaginous-aqueous dispersions m and w are whole numbers, as being preferably and, to this end, ithas been proposed to disperse 1 or 2, and at least one of the three indicated such substances as monoglycerides, for example, valence bonds attached to nitrogen is satisfied monostearin and mono-olein, oleic acid mono- 10 by a radical of the class consisting of alkyls,

ester of diglycerol, laul'yl mono-ether of glycerol, cycloalkyls, alkylols', arallqr'ls, ary'ls, aralkylols,

stearic acid mono-esters of glycols and polyand the radical of a heterocyclic ring of which glycols, in aqueous or oleaginous-aqueous media, the nitrogen is a member.

in the preparation of emollient compositions. A particularly satisfactory sub-group of said It has been found, however, that such substances 1 modifying compounds may be represented by the as-those mentioned above, by way of illustraformula: tion, will not disperse in neutral or acid aqueous solutions or aqueous-oleaginous dispersions to F H:N H:-1I

produce smooth, homogeneous dispersions which will remain in such condition for. appreciable :0 periods of time For example, attempts to form a 5% dispersion of mono-olein in water have not been successful, a mass separating out after only a short period of time.

In accordance with the present invention, the 25, disadvantages which have characterized'former practices are overcome in a highly effective manner. It has been found that when monoglycer- I ides or the like, as set out above'and which are referred toin greater detail below, are utilized :0 m E o CHFCHPNH wherein R is a fatty acid hydrocarbon radical containing from five to seventeen and particularly from seven to thirteen carbon atoms, A isto nitrogen are linked directly. to carbon.'

Representative examples 'of the modifying compounds which are utilized in accordance with the present invention are the following? in conjunction with certain other agents, which r 1 shall herein be designated as modifying com- I pounds, it becomes possible to prepare smooth, (2) v homogeneous emollient compositions which are A 0K stable and which will so remain for very substan- $6 .tiai periods of time. Other advantages emanating from the invention will be pointed out hereinafter. I (a) 0nHu-co-cmi-Nnco -cnr-cnr caHi The modifying compounds may, in general, be i wherein R is an organic radical containing at w c sg#00315; II

designated by the formulae 40 g n (o) cuna-cw-cm-cm-Nn-co-c rs least four, andpreferably from six to fourteen carbon atoms, all: stands for hydrocarbon, for a r l 1 example, alkylene or arylene such as ethylene 55 v or phenylene, Y is hydrogen, alkyl, cycloallwl, E E i alkoxyl, aralkyl, aryl, or alkylol, Z is a residue, 0 l preferablyacarbon-hydrogen residue, ofamono- The modifying compounds are disclosed in or poly-carboxylicacid, preferably aliphatic and greater detail in the patent to Albert K. Epstein preferably containing not more than eight carso and Benjamin B. Harris, No. 2,290,173, issued halogen, and the threevalence bonds attached July 21, 1942, and reference may be made there tO. In the said Patent No; 2,290,173, the modifying compounds areshown to possess antiseptic, bactericidal and germicidal properties. In accordance with the present invention,'in addition to they primary function served by the modifying compounds, namely, to modify the action of the higher fatty acid monoglycerlde and the like so as to permit the production of smooth, homo geneous dispersions, they have the incidental function of imparting some antiseptic, bactericidal and germicidal properties to the compositions in which they are incorporated. No claim is, however, made to such feature in the present invention, such result, as stated above, being incidental to the essential purpose achieved by their use in accordance with' the teachings of the present invention.

The esters of the aliphatic polyhydroxy substances which are used in conjunction with the modifying compounds, as described above. comprise the higher molecular weight carboxylic acid partial esters of aliphatic polyhydroxy substances containing at least one free or unesterined hydroxy group attached to the polyhydroxy nucleus. Representative materialsin this class are mono-.

caprylin, dicaprylin, monolaurin, dilaurin, monomyristin, monopalmitin, mono-olein, monostearin, oleic acid mono-ester of diglycerol, stearic acid mono-ester of diglycerol; lauric, oleic and stearic acid mono-esters of ethylene glycol, diethylene glycol and triethylene glycol;,oleic and stearic acid mono-esters of sorbitol, sorbitan, mannitol and mannitan, and the like.

In'general, the partial esters of the aliphatic polyhydroxy substances may be derived by esteriflcation of any of the following illustrative aliphatic polyhydroxy substances with any of the following illustrative higher molecular weight carboxylic acids. g Aliphatic polyhydroxy substances-glycerol;

I acids, and, the like.

aseaaoe' acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cotton seed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, partially or completely hydrogenated animal and vegetable oils such as those mentioned; oxidized hydrox'y and alpha-hydroxy higher carboxylic, aliphatic and fatty and/or polymerized higher fatty acids or higher fatty acids derived from oxidized and/orpolymerized triglyceride oils; hydroxy acids such as alphahydroxy capric acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid, alpha-hydroxy coconut oil mixed fatty acids, and the like; naphthenic and aromatic acids such, as phthalic acid, benzoic acid, Twitchell fatty acids, naphthoic acid, pyridine carboxylic acid; hydroxy aromatic acids such as salicylic acid, hydroxy benzoic and naphthoic It will be understood that mixtures of any two or more of said acids may be employed if desired and it will also'be appreuse of the former is, therefore, definitely preglucosides; sugar alcohols such as arabitol, mannitol, mannitan, mannide, sorbitol, sorbitan, sor-- bide, and dulcitol; and polyhydroxycarboxylic acid, gluconic acid, glucuronic acid, gulonic acid,

mannonic acid, trihydroxyglutaric acid, glyceric acid, carboxylic oxidation products of polyglyceri ols, others of similar character, and hydroxyethyl and hydroxypropyl ether derivatives of the above. Higher molecular weight carboxylic acidsstraight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic. (including cycloaliphatic) fatty, aromatic, hydroaromatic and araliphatic acids including caproic acid, caprylic acid, pelargonic acid, capric acid, 'sebacic acid, oleic acid; riclnoleic acid, ricinelaidic acid, ricinostearolic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above-mentioned acids or other .ciated that said acids may contain substituent groups such as halogen, ketone and other groups.

Of particular utility are the. fatty acids containing I from 8 to 18 carbon atoms.

I'hep'articularly preferred partial esters of aliphatic polyhydroxy substances for use in accordance with the present invention are the higher molecular .weight fatty acid mono-esters of glycerine, glycols and polyglycols, the stearic acid mono-ester of diethylene glycol being especially satisfactory.

In place of or together with the partial ester of the aliphatic polyhydroxy substances disclosed above, we may use the higher alkyl partial ethers of the aliphatic polyhydroxy substances." Repres'entative examples thereof are lauryl mono-ether of glycerol, myristyl mono-ether of diethylene glycol, decyl mono-ether of diglycerol, hexyl diether of glycerol, lauryl di-ether of diglycerol, cetyl mono-ether of glycerol, oleyl mono-ether of sorbitol, stearyl mono-ether of mannitol, and the like. Generally speaking, the partial esters are more satisfactory than the partial ethers and the ferred.

The following examples are illustrative of compositions falling within the scope of the present invention. It will be understood, however, that the invention is not restricted thereto as'various changes may be made with respect to the combinations of different modifying compounds and partial esters of aliphatic polyhydroxy substances, proportions, emollient products, and the like, all

of which are within the scope of the invention in the light of the guiding principles disclosed herein.

Example I (a) grams of the stearic acid monofester of diethylene glycol and 10 grams of a modifying compound having the formula were heated together at approximately degrees C. until a clear solution was obtained. The mass was then allowed to cool.

(b) A lotion was made by admixing water, mineral oil and the composition of part (a) of this example, in the following proportions by weight: 90% water, 5% mineral oil, 5% composition of part (a) ethylene glycol and '65 grams of a modifying com amples.

Example I! (a) 80 of monostearinwere heated to 120 degrees C. and mixed with 20 grams of a modifying compound -having the formula and the mass was then allowed to cool.

(12) 10 grams of the composition of part (a) of this example, 40 grams of light mineral oil and grams of spermaceti wereheated together. to- Bil-degrees C. whereupon a clear oleaginous solu-.' tion was formed. The same was then added, slowly and with constant stirring to a solution containing 40 cc. of water and 5grams-of tartaric acid, saidsolution also being at 80 degrees C. The mass was continuously stirred during the addition and the stirring was continued until the" resulting dispersion reached room temperature.

The product comprised a heavy, white dispersion,

' and was very useful as a cosmetic.

Example III 35 grams of the stearic acid mono-ester of dipound having the formula were heated and mixed together at approximately 100 degrees C. and then allowed to cool. The resulting composition may be employed to make smooth, homogeneous dispersions of aqueous or aqueous-oleaginous character containing, for example, from 2% to 15% of the composition, based'on the weight of the dispersion.

3 Esrampie IV I 75 grams of the palmitic acid mono-ester of triethylene glycol were heated to about 100 de grees C. and mixed withi25 grams of a modifying compound having the formula erties are. similar to those of the previous ex- As has been pointed out above, and as is clear hydroxy substance incompletely esterified with a fatty acid having from 8 to 18 carbon atoms. and (2) a compound having the formula wherein R is an aliphatic radical containing at least 4 carbon atoms, all: is hydrocarbon, Y is a memlmr selectedfrom the group consisting of hydrogen. alkyl, cycloalkyl, alkoxyl, aralkyl, aryl and alkylol, Z is the carbon-hydrogen residue of a carboxylic acid, A is an anion; m and w are whole numbers, and the three valence bonds attached to nitrogen are linked directly to carbon,

compound (2) exceeding the amount of compound (l) in said emollient composition.

2. Anemollient composition including water and minor proportions of 1) an aliphatic poly- .hydroxy substance incompletely esterifiedwith a fatty acid having from 8 to 18 carbon atoms,

and (2) a compound having the formula wherein R is a hydrocarbon radical containing from 5 to 17 carbon atoms, alk is a hydrocarbon radical, Z is a hydrocarbon radical, A is a halogen,

m is a small whole number, and the three valence and the mass was then allowed to cool. Its propfrom the foregoing examples, the proportions of I the modifying compounds and the partial esters 1 of the aliphatic polyhydroxy substances are sub ject to considerable variation. For most purposes, it is preferred that the ratio of the modifying compounds to the partial esters of the allphatic polyhydroxy substances be of the order of one to ten or one to from ten to twenty. However, the ratio may, in various casesibe reversed, that is, the modifying compounds may exceed the partial esters of thealiphatic polyhydroxy suhstances by ten fold or twenty fold. It will also be, understood that the compositions may contain supplemental ingredients such as perfumes,- dyes, antiseptic agents, and the like. d The proportions of the mixture of modifying compound and partial ester of aliphatic poiyhydroxy substance employed in making the dispersions aresubject to variation, being dependent, among other things, on the potency of the speciflc composition selected, the specific character .of the dispersion in which it is employed, and the exact resul desired. In general, from about 0.5%to 10%, based upon the weight of the diswherein R' is a fatty acid hydrocarbon radicalcontaining from 5 to 17. carbon atoms, A is halo bonds att-i hed to nitrogen are linked directly tov carbon, compoundv (2) exceeding the amount of compound (I? in said emollient composition 3. An -eimillient composition including water and minor proportions of 1) an aliphatic poly- -hydroxy substance incompletely esterified with a fatty acid having from 8 to 18 carbon atoms, and (2) a compound having the formula n-c-m-cnr-cin-Nn-t z-cnrn where R. is a fatty acidhydrocarbon radical containing fron'i' 5 to 17 carbon atoms, A is halogen, and the three valence bonds attached to nitrogen are linked directly to carbon, compound (2) exceeding the amount of compound (1) in said 1 emollient composition.

placed by a' higher moleculanweight aliphatic radical, and (2) a compound. having the formula wherein R is an aliphatic radical containing at least 4 carbon atoms, alk is hydrocarbon, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl and alkylol, Z is the carbon-hydrogen residue of a carboxylic acid, A is an anion, m and w are whole numbers, and the three valence bonds attached to nitrogen are linked directly to carbon.

7. A composition having utility in emollient compositions and the like, comprising (1) an aliphatic polyhydroxy substance at least one but not all of the hydrogens of the hydroxy groups of which are replaced by a higher molecular weight aliphatic radical, and (2) a compound having the formula wherein R is a hydrocarbon radical containing at least '7 carbon atoms, all: is a hydrocarbon radical, Z is a hydrocarbon radical, A is halogen, m is a small whole number, and the three valence bonds attached to nitrogen are linked directly to carbon. 7

.8. A composition having utilityin emollient compositions and the like, comprising (1) an allphatic polyhydroxy substance incompletely esterifled with a fatty acid having from 8 to 18 carbon atoms, and (2) a compound having the formula R-C-O-(alk-NH) ..-o Z-N II l wherein R is a hydrocarbon radical containing from to 17 carbon atoms, alk is a hydrocarbon radical, Z is a hydrocarbon radical, A i halogen, m is a small whole number, and the three valence bonds attached to nitrogen are linked directly to carbon, compound (2) exceeding the amount'of compound (1) in said emollient composition.

9. A composition having utility in emollient compositions and the like comprising (1) an allphatic polyhydroxy substance incompletely esterified with a fatty acid having from 8 to 18 carbon atoms, and (2) a compound having the formula ao-o-onr-cn,-Nn-c-cmn II l o I A where R is a fatty acid hydrocarbon radical conphatic polyhydroxy substance the hydrogen of at,

asaaaee but not all of the hydroxy groups of which is re-' taining from 5 to 17 carbon atoms, A is halogen. and the three valence bonds attached to nitrogen are linked directly to carbon, compound (2) exceeding the amount of compound (1) in said emollient composition. 1

10. A composition having utility in emollient compositions and the like comprising (1) an allleast one but not all of the hydroxy groups of which is replaced by a higher molecular weight aliphatic radical, and (2) a compound havingthe formula R-C-"O-CHr-QHa-NH-(fi-Cllr-Ii where is the acyl radical of a fatty acid having from 8 to 18 carbon atoms.

11. A composition having utility in emollient compositions and the like comprising (1) an allhatic polyhydroxy substance incompletely esterified with a fatty acid having from 8 to 18 carbon atoms, and (2) a compound having the formula where 1. -fiis the acyl radical of a fatty acid having from 8 to 18 carbon atoms.

12. An emollient composition including water and minor proportions of (1) an aliphatic polyhydroxy substance the hydrogen of at least one but not all of the hydroxy groups of which is replaced by a higher molecular weight aliphatic radical, and (2) a quaternary ammonium compound having the formula wherein R is an aliphatic radical containing at 1east'4 carbon atoms, alk is hydrocarbon, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aryl and alkylol, Z is the carbon-hydrogen residue of a carboxylic acid, A is an anion, m and w are whole numbers, and the three valence bonds attached to nitrogen are linked directly to carbon.

13. An emollient composition including water and minor proportions of (1) an aliphatic poly,- hydroxy substance the hydrogen of at least one but not all of the hydroxy groups of which is replaced by a higher molecular weight aliphatic radical, and (2) a compound having the formula where R is a hydrocarbon radical containing at least '7 carbon atoms, alk is a hydrocarbon radical, A is halogen, m is a small whole number, and

the three valence bonds attached to nitrogen are linked directly to carbon.

ALBERT K. EPSTEIN. MORRIS KATZMAN. 

